ORGANIC CHEMISTRY I UNIT 1

HALOALKANES CHAPTER 2

CHAPTER 2 HALOALKANES

INTRODUCTION
This chapter discusses the functional group, classes, IUPAC names, physical
properties, synthesis and chemical properties of haloalkanes.

OBJECTIVES
At the end of this chapter, you should be able to:
1. identify haloalkanes from their functional group, classify them as methyl, primary,
secondary and tertiary, and write their IUPAC names;
2. compare the melting points, boiling points and densities of haloalkanes with aliphatic
hydrocarbons, and the densities of fluoro-, chloro-, bromo- and iodoalkanes;
3. describe the synthesis of haloalkanes from alkanes, alkenes and alkynes;
4. write the mechanisms for nucleophilic substitution (SN1 and SN2) and elimination
reactions (E1 and E2), and identify haloalkanes that undergo these reactions and their
order of reactivity; and
5. describe the synthesis of two organometallic compounds from haloalkanes, namely
Grignard reagents and organolithiums.

2.1 CLASSIFICATION AND NOMENCLATURE

In your opinion, how is haloalkanes different from hydrocarbons?

Haloalkanes (R-X) have one or more halogen atoms (F, Cl, Br or I) as their functional
group. Examples are CH3F, CH2Cl2, C2H5Br, and CHI3. They are classed as methyl (CH3-
X), primary (RCH2-X), secondary (R2CH-X), or tertiary (R3C-X) haloalkane.

The IUPAC name is “haloalkane” (halo is fluoro, chloro, bromo or iodo). The location
of the halogen in the main chain is indicated by the lowest number. Examples:

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H H H H H CH3 H H
H C C C C H H C C C C H
H Br H H H CI H H

CH3-CH(Br)-CH2CH3 (CH3)2C(CI)-CH2CH3
2-bromobutane 2-chloro-2-methylbutane
(secondary haloalkane) (tertiary haloalkane)

Example 2.1

Classify and name the following haloalkane.

CH3 H
CH3 C CH2 C Br
CH2 CH CH3

CH3 CH3
Answer
Class : secondary haloalkane
IUPAC name : 3-bromo-2,5,5-trimethylheptane

2.2 PHYSICAL PROPERTIES

Haloalkanes are polar molecules. Thus, their melting and boiling points are higher than
hydrocarbons of similar molar mass. For example, the boiling point of CH 3CH 2Cl
(chloroethane, molar mass 64.5) is 12 oC while that of CH 3(CH 2)2CH 3 (butane, molar
mass 58) is 0 oC. They are also more soluble in water.

Their densities follow the trend: R-F < R-Cl < R-Br < R-I. For example, the density of
CH3CH2-F is 0.72, CH 3CH2-Cl is 0.90, CH3CH2-Br is 1.46, and CH 3CH 2-l is 1.94.

2.3 SYNTHESIS
Haloalkanes may be synthesized by (a) halogenation of alkanes, and (b)
halogenation or hydrohalogenation of alkenes or alkynes. These were discussed
in Chapter 1.

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2.4 CHEMICAL PROPERTIES

Haloalkanes undergo nucleophilic substitution and elimination reactions.

2.4.1 Nucleophilic Substitution Reactions

The R-X bond of haloalkanes is polar (R δ + –X δ - ) because halogens are more

electronegative than carbon. Thus, they react with nucleophiles (electron-rich species
such as OH –, H 2O, NH3, and CN–), which attack the carbocation (Rδ+).

(a) Reaction with aqueous sodium hydroxide, NaOH(aq)

Haloalkanes (R–X) reacts with aqueous NaOH to form alcohols (R-OH). The nucleophiles
are H2O and OH–. The general equation and an example are:

R-X + NaOH(aq)
∆ R-OH + NaX

CH3Cl + NaOH(aq) ∆ CH3-OH + NaCl

chloromethane methanol

(b) Reaction with ammonia (NH3)

Haloalkanes (R–X) reacts with NH3 to form primary amines (R–NH2).The nucleophile is
NH3. The general equation and an example are:

R–X + 2NH3 ∆ R–NH2 + NH4X

CH3CH2–Cl + 2NH3 ∆ CH3CH2-NH2 + NH4Cl

chloroethane ethanamine

(c) Reaction with potassium cyanide (KCN)

Haloalkanes (R–X) reacts with KCN in ethanol (as solvent) to form alkanenitriles (R–
CN). The nucleophile is CN–. The general equation and an example are:

CH3CH2OH
R–X + KCN R–CN + KX
∆

CH3-CH-CH2–Cl + KCN ∆ CH3-CH-CH2–CN + KCl

| |
CH3 CH3
1-chloro-2-methylpropane 3-methylbutanenitrile

Note:
1. The product has one more carbon than the reactant.
2. The reaction is limited to primary haloalkanes. Secondary and (especially) tertiary
haloalkanes undergo elimination reaction with KCN (to be discussed later).

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2.4.2 Nucleophilic Substitution Mechanisms

(a) Unimolecular nucleophilic substitution (SN1)

SN1 reaction is favored by tertiary haloalkanes because they form more stable tertiary
carbocations. For example:
(CH3)2CBrCH2CH3 + NaOH (CH3)2C(OH)CH2CH3 + NaBr
2-bromo-2-methylbutane 2-methyl-2-butanol

The nucleophiles are OH– and H2O. The rate equation and mechanism are:
Rate = k [R–X]

and,

The order of reactivity is R3C–X > R2CH–X > RCH2–X > CH3–X

(b) Bimolecular nucleophilic substitution (SN2)

SN2 reaction is favored by primary haloalkanes. For example:
CH3CH2–Cl + 2 NH3 CH3CH2–NH2 + NH4Cl
chloroethane ethanamine

The nucleophile is NH3. The rate equation and mechanism are:

Rate = k[R–X] [Nu]

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The nucleophile attacks the halogenated carbon from the end opposite to Cl. Thus,
the size of the alkyl group bonded to the halogenated carbon determines the reactivity
of haloalkanes. The order is:

RCH 2-X > R 2CH-X > R 3C-X

However, primary haloalkanes with large alkyl groups (for example (CH 3)3CCH 2Br) will
not undergo S N2 reaction due to steric hindrance.

The reaction results in inversion of configuration.

Example 2.2

Does 2-chloropropane react with NaOH(aq) by S N1 or S N2 mechanism? Explain

your answer and write the equation for the reaction.

Answer

2-chloropropane (CH 3CHClCH 3) reacts by both S N1 and S N2 mechanisms. This

is because it is a secondary haloalkane.

CH 3CHClCH 3 + NaOH CH 3CH(OH)CH 3 + NaCl

2.4.3 Elimination Reactions

Haloalkanes eliminate HX to form alkenes when they react with a strong base, such
as OH –, OR –, CN – (refer to Chapter 1). The mechanisms are unimolecular elimination
(E1) and bimolecular elimination (E2).

(a) Unimolecular elimination (E1)

E1 reaction is favored by tertiary haloalkanes because they form more stable tertiary
carbocations. For example:
CH3CH2OH
(CH 3) 2CBrC(CH 3) 3 + KOH CH 2=C(CH 3)C(CH 3)3 + KBr + H2O
2-bromo-2,3,3-trimethylbutane 2,3,3-trimethyl-1-butene

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The base is OH–. The rate equation and the mechanism are:
Rate = k [R-X])

Note:
1. The strong base abstracts H atom adjacent to the positively”charge carbon.
2. The order of reactivity: R3C-X > R2CH-X. Primary haloalkanes do not undergo E1
reactions.
3. A less stable carbocation formed may rearranges to a more stable carbocation
(refer to Chapter 1).

(b) Bimolecular elimination (E2)

E2 reactions occur when very strong bases are used. For example:

CH3CH2OH
CH3CH 2–Cl + K–CN CH 2=CH 2 + HCN + KCl
chloroethane ethene

The strong base is CN– ion. The rate equation and the mechanism are:
Rate = k[R–X][base]

Note:
1. The strong base abstracts H atom adjacent to the halogenated carbon.
2. The order of reactivity: R3C-X > R2CH-X > RCH2-X (same as E1).
3. The reaction occurs in one step. Thus, rearrangement does not happen since
carbocations are not formed.

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Example 2.3

Explain why chloromethane and 2,2-dimethyl-1-chloropropane do not undergo E1

or E2 reaction with any strong base?

Answer

Chloromethane, CH3Cl is a methyl haloalkane, while 2,2-dimethyl-1-chloropropane,

(CH3)3C-CH2Cl, is a primary haloalkane. Both haloalkanes cannot undergo E1 or E2
reaction because they do not have any H atom adjacent to the halogenated carbon.

2.4.4 Synthesis of Organometallic Compounds

Organometallic compounds have carbon-metal bonds.

(a) Grignard reagents, R-Mg-X

Grignard reagents (R–Mg–X; X either Cl or Br) are synthesized from the reaction of
haloalkanes (R-X) with magnesium (Mg) in anhydrous diethyl ether. For example,

ether
CH3-CH2-CH2-Br + Mg CH3-CH2-CH2-Mg-Br
1-bromopropane propylmagnesium bromide

Grignard reagents may be used to synthesize alkanes (Chapter 1), alcohols (Chapter 3),
and carboxylic acids (Chapter 6).

(b) Organolithiums, R-Li

Organolithiums (R-Li) are synthesized from the reaction of haloalkanes (R-X) with lithium
(Li) in organic solvents. For example:

CH3CH2CH2-Br + 2 Li CH3CH2CH2-Li + LiBr

1-bromopropane propyllithium

The reactions of organolithiums are similar to Grignard reagents, but they are more
reactive.

Exercise 2.1

1. Classify the following haloalkane as methyl, primary, secondary or tertiary,

and write its IUPAC name.
(a) CH2BrCH3
(b) (CH3)3CCl

(c)

(d) CH2I

(e) (CH3CH2)2CHBr

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2. Write the structural formula of the following haloalkane.

(a) 1-chloro-2,3-diethylpentane
(b) 2-(bromomethyl)heptane
(c) 1-bromo-1-propylcyclopentane

3. Write an equation for the following reaction:

(a) (CH3)3CCl with NaOH(aq)
(b) 1-chloro-4-ethylhexane with excess NH3
(c) (chloromethyl)cyclopentane with KCN in ethanol
(d) 1-chloro-2-methylbutane with Mg in anhydrous diethyl ether

4. Write the order of reactivity of the following haloalkanes towards SN1

and E1 reactions.
CH3Cl, CH3CH2Cl, (CH3)2CHCl, (CH3)3CCl

5. Name the reagent and explain the mechanism for the reaction of
chloroethane with:
(a) KOH(aq) (b) KOH/CH3CH2OH

6. The rate equation for the reaction of (CH2CH3)3CBr with aqueous NaOH
is given below. Discuss the mechanism of the reaction.
Rate = k [(CH2CH3)3CBr].

7. Discuss the mechanism for the reaction of (CH3)3CCl with KCN in

ethanol.

8. Explain why (CH3CH2)3C-CH2Cl does not react with aqueous or ethanolic

NaOH.

9. Write the structural formulas of compounds A – J, and the reaction

equations, based on the following informations:
(a) Hydrocarbon A reacts with chlorine gas when exposed to ultraviolet
light to form compound B. Compound B reacts with aqueous KOH
to form CH3CH(OH)CH3.
(b) Compound C reacts with hot aqueous NaOH to form compound D
which forms propene in the presence of concentrated sulphuric
acid.
(c) 2-methyl-1-butene reacts with HBr in the absence of a peroxide to
form compound E. Compound E reacts with KOH in ethanol to
form compound F and compound G.
(d) Compound H reacts with HBr to form compound I which reacts
with excess NH3 to form CH3CH2CH(NH2)CH2CH3.
(e) Compound J reacts with Mg in anhydrous diethyl ether to form
(CH3)2CHCH2MgBr.

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10. Write a reaction equation for the synthesis of a suitable Grignard reagent
to be used for the synthesis of 2-methylbutane.

11. What are the chemicals needed to prepare isopropyllithium? Write the
equation for the reaction.

SUMMARY
• Haloalkanes, R–X (X = F, Cl, Br or I) are classed as either methyl (CH3–X), primary
(RCH2–X), secondary (RR’CH–X), or tertiary (RR’R–C–X).
• Their melting points, boiling points and solubilities in water are higher than the
corresponding hydrocarbons.
• They may be prepared by halogenation of alkanes, alkenes, and alkynes, and by
hydrohalogenation of alkenes and alkynes.
• They undergo nucleophilic substitution (SN1 and SN2) and elimination (E1 and E2)
reactions. The order of reactivity is:
– S N1: methyl < primary < secondary < tertiary
– S N2: methyl > primary > secondary > tertiary
– E1 : secondary < tertiary
– E2 : primary < secondary < tertiary
• Haloalkanes may be used to synthesize Grignard reagents and organolithiums.

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